Claims
- 1. An improved process for the free-radical polymerization of at least one unsaturated vinylic monomer to form a polymer whose molecular architecture includes at least 10% having branches upon branches and a polymerizable vinyl-terminated end group, comprising contacting
- (i) one or more vinylic monomers having the formula CH.sub.2 .dbd.CYZ, and
- (ii) a chain transfer agent of formula CH.sub.2 .dbd.CQ(CH.sub.2 --X), wherein:
- Y is selected from the group consisting of OR, O.sub.2 CR, halogen, CO.sub.2 H, COR, CO.sub.2 R, CN, CONH.sub.2, CONHR, CONR.sub.2 and R';
- Z is selected H, CH.sub.3, or CH.sub.2 OH provided at least 85.3 mole percent of the (i) has Z=H;
- R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen, and the number of carbons in said alkyl groups is from 1 to 12; and
- R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen;
- X is selected from --(CUY--CH.sub.2).sub.n --Z', S(O)R, S(O).sub.2 R, SnR.sub.3, halogen, R.sup.2 and R.sup.3 ;
- U is selected from H and R;
- Q is selected from Y, or in the case where X is halogen, Y and H;
- Z' is selected from H, SR.sup.1, S(O)R, S(O).sub.2 R, R.sup.2 and R.sup.3 ;
- n is.gtoreq.1;
- R is selected from the group substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
- R.sup.1 is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
- R.sup.2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR.sup.1, O.sub.2 CR, halogen, CO.sub.2 H and salts thereof, CO.sub.2 R, CN, CONH.sub.2, CO.sub.2 NHR, CONR.sub.2 ;
- R.sup.3 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, and P(O)R.sub.2 groups wherein the substituent(s) are independently selected from R, OR.sup.1, O.sub.2 CR, halogen, CO.sub.2 H and salts thereof, CO.sub.2 R, CN, CONH.sub.2, CO.sub.2 NHR, CONR.sub.2 ;
- wherein the improvement comprises obtaining higher yields of polymer having the branch-upon-branch architecture and polymerizable vinylic chain termini, and a higher density of branches upon branches in that polymer by optimizing the polymerization in the following way: select step III and at least one of I; II; I and IV; and II and IV from steps:
- I--decreasing reactivity ratios of (i) and the resulting vinylic-terminated macromonomers and polymers toward 0;
- II--selecting the ratio of(i)/(ii) between 7.11 and 100, dependent on t he values of I, III and IV;
- III--increasing the conversion of (i) and (ii) from 80% toward 100%;
- IV--increasing the temperature from 50.degree. C. toward 150.degree. C.
- 2. A process according to claim 1 wherein Z=H.
- 3. A process according to claim 1 wherein X=.paren open-st.CUY--CH.sub.2).sub.n --Z'.
- 4. A process according to claim 1 wherein, in (i), Z=H and, in (ii), X=.paren open-st.CUY--CH.sub.2).sub.n --Z'.
- 5. A process according to claim 1 wherein Z' is substituted alkyl, aryl, aralkyl, alkaryl, organosilyl wherein the reactive substituent(s) are independently selected from the group carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino and halogen.
- 6. A process according to claim 3 wherein:
- Z is H;
- Q is CO.sub.2 R; and the molar ratio if (i)/(ii) is 5 to 30; and conversion of each of (i) and (ii) is 85 to 100%.
- 7. A composition of matter comprising a polymer having a branch-upon-branch structure and a polymerizable olefinic end group, having the structure: ##STR3## B"=X, B', H, CH.sub.3, CH.sub.2 CHR.sup.1 CH.sub.3, or CH.sub.2 CMeR.sup.2 CH.sub.3,
- X is selected from --(CUY--CH.sub.2).sub.n --Z', S(O)R, S(O).sub.2 R, SnR.sub.3, halogen, R.sup.2 and R.sup.3, where Z' is selected from H, SR.sup.1, S(O)R, S(O).sub.2 R, R.sup.2 and R.sup.3 ;
- Y is selected from the group consisting of OR, O.sub.2 CR, halogen, CO.sub.2 H, COR, CO.sub.2 R, CN, CONH.sub.2, CONHR, CONR.sub.2 and R',
- Z is selected H, CH.sub.3 or CH.sub.2 OH;
- where:
- R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxyl acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen;
- R.sup.1 is selected from the group H, substituted and unsubstituted alkyl, aryl, aralkyl, alkaryl and organosilicon groups wherein the substituent(s) are independently from the group carboxyl, epoxy, hydroxyl, alkoxy, amino and halogen;
- R.sup.2 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, sulfate groups wherein the substituent(s) are independently selected from R, OR.sup.1, O.sub.2 CR, halogen, CO.sub.2 H and salts thereof, CO.sub.2 R, CN, CONH.sub.2, CO.sub.2 NHR, CONR.sub.2 ;
- R.sup.3 is selected from the group free radical initiator-derived fragments of substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, organosilyl, alkoxyalkyl, alkoxyaryl, and P(O)R.sub.2 groups wherein the substituent(s) are independently selected from R, OR.sup.1, O.sub.2 CR, halogen, CO.sub.2 H and salt thereof, CO.sub.2 R, CN, CONH.sub.2, CO.sub.2 NHR, CONR.sub.2 ;
- n=1-20, m=0-5, p=0-20; n+m+p.gtoreq.2;
- and if m>1, then the m insertions are not consecutive.
- 8. The composition according to claim 7 wherein X is --(CUY--CH.sub.2).sub.n --Z' where U is selected from H and R.
Parent Case Info
This application is a .sctn.371 national phase application of PCT/US97/02913 filed on Feb. 18, 1997, which takes priority from U.S. provisional application Ser. No. 60/012,131 filed on Feb. 23, 1996.
PCT Information
| Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
| PCT/US97/02913 |
2/18/1997 |
|
|
8/19/1998 |
8/19/1998 |
| Publishing Document |
Publishing Date |
Country |
Kind |
| WO97/31031 |
8/28/1997 |
|
|
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| Number |
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Date |
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Janowicz et al. |
Jul 1987 |
|
| 5362813 |
Antonelli et al. |
Nov 1994 |
|
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Berge et al. |
Nov 1994 |
|
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Antonelli et al. |
Jun 1998 |
|
Foreign Referenced Citations (1)
| Number |
Date |
Country |
| 73-034882 |
|
JPX |
Non-Patent Literature Citations (2)
| Entry |
| Salamone, Polymeric Materials Encyclopedia, 3, 1799-1830, 1996. |
| Salamone, Polymeric Materials Encyclopedia, 5, 3049-3185, 1996. |
Patent Grant
6100350
